Methanol (CH$_3$OH) is found to be abundant and widespread towards the Central Molecular Zone, the inner few hundred parsecs of our Galaxy. Its origin is, however, not fully understood. It was proposed that the high cosmic ray ionisation rate in this region could lead to a more efficient non-thermal desorption of this species formed on grain surfaces, but it would also mean that this species is destroyed in a relatively short timescale. In a first step, we run chemical models with a high cosmic ray ionisation rate and find that this scenario can only reproduce the lowest abundances of methanol derived in this region ($\sim$10$^{-9}$-10$^{-8}$). In a second step, we investigate another scenario based on episodic explosions of grain mantles. We find a good agreement between the predicted abundances of methanol and the observations. We find that the dominant route for the formation of methanol is through hydrogenation of CO on the grains followed by the desorption due to the grain mantle explosion. The cyclic aspect of this model can explain the widespread presence of methanol without requiring any additional mechanism. We also model silicon monoxide (SiO), another species detected in several molecular clouds of the Galactic Centre. An agreement is found with observations for a high depletion of Si (Si/H $\sim$ 10$^{-8}$) with respect to the solar abundance.
Methanol ice is embedded in interstellar ice mantles present in dense molecular clouds. We aim to measure the sputtering efficiencies starting from different ice mantles of varying compositions experimentally, in order to evaluate their potential impact on astrochemical models. The sputtering yields of complex organic molecules is of particular interest, since few mechanisms are efficient enough to induce a significant feedback to the gas phase. We irradiated methanol and carbon dioxide ice mixtures of varying ratios with swift heavy ions in the electronic sputtering regime. We monitored the e…
We present ALMA maps of the starless molecular cloud core Ophiuchus/H-MM1 in the lines of deuterated ammonia (ortho-NH2D), methanol (CH3OH), and sulphur monoxide (SO). The dense core is seen in NH2D emission, whereas the CH3OH and SO distributions form a halo surrounding the core. Because methanol is formed on grain surfaces, its emission highlights regions where desorption from grains is particularly efficient. Methanol and sulphur monoxide are most abundant in a narrow zone that follows the eastern side of the core. This side is sheltered from the stronger external radiation field coming fro…
We carry out Monte-Carlo simulation to study deuterium enrichment of interstellar grain mantles under various physical conditions. Based on the physical properties, various types of clouds are considered. We find that in diffuse cloud regions, very strong radiation fields persists and hardly a few layers of surface species are formed. In translucent cloud regions with a moderate radiation field, significant number of layers would be produced and surface coverage is mainly dominated by photo-dissociation products such as, C,CH_3,CH_2D,OH and OD. In the intermediate dense cloud regions (having n…
Mantles of iced water, mixed with CO, H2CO, and CH3OH are formed during the so called prestellar core phase. In addition, radicals are also thought to be formed on the grain surfaces, and to react to form complex organic molecules later on, during the warm-up phase of the protostellar evolution. We aim to study the formation of the grain mantles during the prestellar core phase and the abundance of H2CO, CH3OH, and radicals trapped in them. We have developed a macrosopic statistic multilayer model that follows the formation of grain mantles with time and that includes two effects that may incr…
We report the first high angular resolution imaging (3.4\arcsec $\times$ 3.0\arcsec) of deuterated formaldehyde (HDCO) toward Orion--KL, carried out with the Submillimeter Array (SMA). We find that the spatial distribution of the formaldehyde emission systematically differs from that of methanol: while methanol is found towards the inner part of the region, HDCO is found in colder gas that wraps around the methanol emission on four sides. The HDCO/H$_2$CO ratios are determined to be 0.003--0.009 within the region, up to an order of magnitude higher than the D/H measured for methanol. These fin…
After more than 30 years of investigations, the nature of gas-grain interactions at low temperatures remains an unresolved issue in astrochemistry. Water ice is the dominant ice found in cold molecular clouds, however, there is only one region where cold (~10 K) water vapor has been detected - L1544. This study aims to shed light on ice desorption mechanisms under cold cloud conditions by expanding the sample. The clumpy distribution of methanol in dark clouds testifies to transient desorption processes at work -- likely to also disrupt water ice mantles. Therefore, the Herschel HIFI instrumen…
Cold gas-phase water has recently been detected in a cold dark cloud, Barnard 5 located in the Perseus complex, by targeting methanol peaks as signposts for ice mantle evaporation. Observed morphology and abundances of methanol and water are consistent with a transient non-thermal evaporation process only affecting the outermost ice mantle layers, possibly triggering a more complex chemistry. We present the detection of the Complex Organic Molecules (COMs) acetaldehyde and methyl formate as well as formic acid and ketene, and the tentative detection of di-methyl ether towards the methanol hots…
Extremely high deuteration of several molecules have been observed around low mass protostars since a decade. Among them, formaldehyde and methanol present particularly high deuteration, with observations of abundant doubly and triply deuterated forms. Both species are thought to be mainly formed on interstellar grains during the low temperature and dense pre-collapse phase by H and D atom additions on the iced CO. We present here a theoretical study of the formaldehyde and methanol deuteration obtained with our gas-grain model, GRAINOBLE. This model takes into account the multilayer nature of…
Under cold conditions in dense cores, gas-phase molecules and atoms are depleted from the gas-phase to the surface of interstellar grains. Considering the time scales and physical conditions within these cores, a portion of these molecules has to be brought back into the gas-phase to explain their observation by milimeter telescopes. We tested the respective efficiencies of the different mechanisms commonly included in the models. We also tested the addition of sputtering of ice grain mantles via a collision with cosmic rays in the electronic stopping power regime. The ice sputtering induced b…
We present MERLIN observations of OH, water and methanol masers towards the young high mass stellar object IRAS 20126+4104. Emission from the 1665-MHz OH, 22-GHz H_2O and 6.7-GHz CH_3OH masers is detected and all originates very close to the central source. The OH and methanol masers appear to trace part of the circumstellar disk around the central source. The positions and velocities of the OH and methanol masers are consistent with Keplerian rotation around a central mass of ~ 5 Msun. The water masers are offset from the OH and methanol masers and have significantly changed since they were l…
Recent observations indicate that organic molecules are prevalent towards starless and prestellar cores. Deuteration of these molecules has not been well-studied during the starless phase. Published observations of singly-deuterated methanol, CH$_2$DOH, have only been observed in a couple of well-studied, dense and evolved prestellar cores (e.g. L1544, L183). Since the formation of gas-phase methanol during this cold phase is believed to occur via desorption from the icy grain surfaces, observations of CH$_2$DOH may be useful as a probe of the deuterium fraction in the ice mantles of dust grai…
In dense molecular clouds, interstellar grains are covered by mantles of iced molecules. The formation of the grain mantles has two important consequences: it removes species from the gas phase and promotes the synthesis of new molecules on the grain surfaces. The composition of the mantle is a strong function of the environment which the cloud belongs to. Therefore, clouds in high-zeta galaxies, where conditions -like temperature, metallicity and cosmic rays flux- are different from those in the Milky Way, will have different grain mantles. In the last years, several authors have suggested th…
We present new radio-frequency interferometric maps of emission from the 14NH3, 15NH3, and 14NH2D isotopologues of ammonia, and the 12CH3OH and 13CH3OH isotopologues of methanol toward Sgr B2(N). With a resolution of ~3'' (0.1 pc), we are able to spatially resolve emission from two hot cores in this source and separate it from absorption against the compact HII regions in this area. The first (N1) is the well-known v = 64 km/s core, and the second (N2) is a core 6'' to the north at v = 73 km/s. Using emission from 15NH3, and hyperfine satellites of 14NH3 metastable transitions we estimate the …
We present a model for the formation of large organic molecules in dark clouds. The molecules are produced in the high density gas-phase that exists immediately after ice mantles are explosively sublimated. The explosions are initiated by the catastrophic recombination of trapped atomic hydrogen. We propose that, in molecular clouds, the processes of freeze-out onto ice mantles, accumulation of radicals, explosion and then rapid (three-body) gas-phase chemistry occurs in a cyclic fashion. This can lead to a cumulative molecular enrichment of the interstellar medium. A model of the time-depende…
The relative abundances of singly-deuterated methanol isotopologues, [CH$_{2}$DOH]/[CH$_{3}$OD], in star-forming regions deviate from the statistically expected ratio of 3. In Orion KL, the nearest high-mass star-forming region to Earth, the singly-deuterated methanol ratio is about 1, and the cause for this observation has been explored through theory for nearly three decades. We present high-angular resolution observations of Orion KL using the Atacama Large Millimeter/submillimeter Array to map small-scale changes in CH$_{3}$OD column density across the nebula, which provide a new avenue to…
At low temperatures (10 K), hydrogen atoms can diffuse quickly on grain ice mantles and frequently encounter hydrogen molecules, which cover a notable fraction of grain surface. The desorption energy of H atoms on H2 substrates is much less than that on water ice. The H atom encounter desorption mechanism is adopted to study the enhanced desorption of H atoms on H2 substrates. Using a small reaction network, we show that the steady-state surface H abundances predicted by the rate equation model that includes H atom encounter desorption agree reasonably well with the results from the more rigor…
We observed OH, H$_2$O, HN$_3$, C$^{18}$O, and C$_I$ towards the +50 km/s cloud (M-0.02-0.07), the CND and the +20 km/s (M-0.13-0.08) cloud in the Sgr A complex with the VLA, Odin and SEST. Strong OH absorption, H$_2$O emission and absorption lines were seen at all three positions. Strong C$^{18}$O emissions were seen towards the +50 and +20 km/s clouds. The CND is rich in H$_2$O and OH, and these abundances are considerably higher than in the surrounding clouds, indicating that shocks, star formation and clump collisions prevail in those objects. A comparison with the literature reveals that …
The collisional pumping of CH3OH and OH masers in non-dissociative C-type shock waves is studied. The chemical processes responsible for the evolution of molecule abundances in the shock wave are considered in detail. The large velocity gradient approximation is used to model radiative transfer in molecular lines. We present calculations of the optical depth in maser transitions of CH3OH and OH for a grid of C-type shock models that vary in cosmic ray ionization rate, gas density and shock speed. We show that pre-shock gas densities $n_{H,tot} = 2 \times 10^4-2 \times 10^5$ cm$^{-3}$ are optim…
A magnetohydrodynamic model of a steady, transverse C-type shock in a dense molecular cloud is presented. A complete gas-grain chemical network is taken into account: the gas-phase chemistry, the adsorption of gas species on dust grains, various desorption mechanisms, the grain surface chemistry, the ion neutralization on dust grains, the sputtering of grain mantles. The population densities of energy levels of ions CI, CII and OI and molecules H$_2$, CO, H$_2$O are computed in parallel with the dynamical and chemical rate equations. The large velocity gradient approximation is used in the lin…
The role of the pre-exponential factor on temperature programmed desorption spectra: A computational study of frozen species on interstellar icy grain mantles
Observations of gaseous complex organic molecules (COMs) in cold starless and prestellar cloud cores require efficient desorption of the COMs and their parent species from icy mantles on interstellar grains. With a simple astrochemical model, we investigate if mechanical removal of ice fragments in oblique collisions between grains in two size bins (0.01 and 0.1 micron) can substantially affect COM abundances. Two grain collision velocities were considered - 10 and 50 meters per second, corresponding to realistic grain relative speeds arising from ambipolar diffusion and turbulence, respective…
In this paper we use observations of molecular tracers in metal rich and alpha-enhanced galaxies to study the effect of abundance changes on molecular chemistry. We selected a sample of metal rich spiral and star bursting objects from the literature, and present here new data for a sample of early-type galaxies (ETGs). We conducted the first survey of CS and methanol emission in ETGs, detecting 7 objects in CS, and 5 in methanol emission. We find evidence to support the hypothesis that CS is a better tracer of dense star-forming gas than HCN. We suggest that the methanol emission in these sour…
Chemical models and experiments indicate that interstellar dust grains and their ice mantles play an important role in the production of complex organic molecules (COMs). To date, the most complex solid-phase molecule detected with certainty in the ISM is methanol, but the James Webb Space Telescope (JWST) may be able to identify still larger organic species. In this study, we use a coupled chemo-dynamical model to predict new candidate species for JWST detection toward the young star-forming core Cha-MMS1, combining the gas-grain chemical kinetic code MAGICKAL with a 1-D radiative hydrodynami…
We report the first detection of the phosphorus monoxide ion (PO$^{+}$) in the interstellar medium. Our unbiased and very sensitive spectral survey towards the G+0.693$-$0.027 molecular cloud covers four different rotational transitions of this molecule, two of which ($J$=1$-$0 and $J$=2$-$1) appear free of contamination from other species. The fit performed, assuming Local Thermodynamic Equilibrium conditions, yields a column density of $N$=(6.0$\pm$0.7)$\times$10$^{11}$ cm$^{-2}$. The resulting molecular abundance with respect to molecular hydrogen is 4.5$\times$10$^{-12}$. The column densit…
